1,2,3,4,5,6,7,8-octahalo-3,7-tricyclo(4.3.0.1**2,5) decadiene-9,10-dione diketals



United States Patent 3,429,8981,2,3,4,5,6,7,8-0CTAHAL0-3,7-TRICYCLO[4.3.0.1 DECADIENE-9,10-DIONEDIKETALS Wen-Hsuan Chang, Gibsonia, Pa., assignor to PPG Industn'es,Inc., a corporation of Pennsylvania N 0 Drawing. Continuation-impart ofapplication Ser. No.

234,846, Nov. 1, 1962. This application Apr. 10, 1967, Ser. No. 629,402US. Cl. 260-3403 6 Claims Int. Cl. C0711 13/04, 15/14, 15/12 ABSTRACT OFTIDE DISCLOSURE This application relates to compounds produced from thereaction of a hexahalocyclopentadiene and a polyol having hydroxylgroups on adjacent carbon atoms corresponding to the formulae:

Formula B Formula C i i in- Formula D 3,429,898 Patented Feb. 25, 1969where R R and R are as above.

or the structure:

CROSS-REFERENCES TO RELATED APPLICATIONS This application is acontinuation-in-part of US. application Ser. No. 234,846, filed Nov. 1,1962, now abandoned.

STATE OF THE PRIOR ART DESCRIPTION OF THE INVENTION It has now beenfound that the reaction of hexahalocyclopentadiene with ethylene glycolor a polyol of the ethylene glycol type, i.e., having hydroxyl groups onadjacent carbon atoms, can be carried out in such a way as to produceseveral products quite different from that reported in the abovearticle. The temperature of the reaction and the amount of base catalystemployed determines the particular nature of the product obtained.

While the compounds referred to are basically all produced fromhexahalocyclopentadiene and a polyol having adjacent hydroxyl groups inthe presence of a base, they correspond to several general formulaewhich are set forth below:

Ra Ra Formula C Formula D In the above formulae, X represents chlorineor bromine and R R and R are each selected from the class consisting ofhydrogen and alkyl, cycloalkyl, aryl, alkoxyalkyl, aryloxyalkyl andhydroxyalkyl radicals usually having up to 20 carbon atoms, andpreferably 1 to carbon atoms. R, is either the structure:

where R R and R are as above.

In the foregoing Formula B and Formula C, it is to be noted that thesubstituents designated as R R and R occur more than once in eachformula. In these instances, each R group may refer to a differentradical selected from the group set forth, and each R and each R maysimilarly be different. Such compounds are obtained, for example, whenproduced by a method in which successive reactions with an alcohol areemployed and a different alcohol is used' in each step. Compounds ofthis type are included within the scope of the various embodiments ofthe invention disclosed and claimed herein.

In producing the compounds of the formulae set forth above, any polyolhaving hydroxyl groups attached to adjacent carbon atoms can beemployed. Such polyols correspond to the formula:

or the structure:

where R R and R are as defined above, these radicals in the polyolcorrespond to those in the above formulae. Examples of such polyols usedto produce the various compounds above include aliphatic polyols such asethylene glycol, 1,2-propanediol, 1,2-butanedio1, 2-methyl-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,2-hexanediol,5,6-decanediol, 2 methyl3,4-pentanediol and 2,2-dimethyl-3,4-butanediol;alicyclic polyols such as cyclohexyl-1,2-ethanediol; aryl-substitutedpolyols such as phenyl-1,2-ethanediol; alkoxy-substituted polyols suchas 1-methoxy-2,3-propanediol; aryloxy-substituted polyols such as1-phenoxy-2,3-propanediol; and polyols containing additional hydroxylgroups in addition to those on the adjacent carbon atoms, such as1,2,6-hexanetriol. In each instance, the polyol must have at least 2carbon atoms, and for most purposes it is preferred to use polyolshaving a total of between 2 and 30 carbon atoms and in which each Rgroup is either hydrogen or alkyl of up to 20 carbon atoms. It has beenfound further that the reaction is best carried out with polyols inwhich the hydroxyl groups are both bonded to either primary or secondarycarbon atoms, i.e., polyols in which R is hydrogen.

The alcohols employed in preparing the compounds of this invention maycontain additional substituents which do not prevent the reaction. Ascan be seen from the above, even compounds having more than two hydroxylgroups may be employed. The preferred alcohols comprise compoundscontaining only carbon, hydrogen and oxygen.

Hexahalocyclopentadiene, as used throughout the specification, refers toa chloroor bromo-substituted cyclopentadiene, for example,hexachlorocyclopentadiene or hexabromocyclopentadiene.

The reactions to produce the compounds of this invention arebase-catalyzed. While essentially any base catalyst, as that term isunderstood in the art, can be used, it is preferred to employ inorganicbases, including the hydroxides, alkoxides and oxides of metals such aslithium, potassium, sodium, calcium, magnesium and the like. The metalsthemselves, e.g., metallic sodium, can also be employed, and providequite satisfactory results. Organic bases such as amines are lesssatisfactory, since they tend to reduce the yield by promoting sidereactions which compete with the desired reaction. The most desirablebases from an economic standpoint are the hydroxides of the alkalimetals and these also provide the best results.

As is more fully set forth hereinbelow, the amount of base employed, aswell as the temperature at which the reaction is carried out, determinesthe particular nature of the product resulting from the reaction of thehexahalocyclopentadiene and the polyol. Aside from these, however, otherreaction conditions are not critical and may be varied widely. Forexample, the reaction can be carried out in the presence of a solvent ifdesired, although quite often the excess polyol orhexahalocyclopentadiene is used as the only solvent. Other inertsolvents such as ethylene glycol dimethylether, diethylene glycoldimethylether, tetrahydrofuran, acetamide, and the like, can be usedwith similar effectiveness, and when the polyol employed is a solid, itis often desirable to have such a solvent present.

The compounds corresponding to Formula A above are produced by thereaction of hexahalocyclopentadiene with a polyol in the presence of abase, as defined above. The temperature at which the reaction is carriedout is below about 50 C. and preferably below about 35 C. in order toobtain the product in good yield. The temperature may also be below roomtemperature, for instance, 0 C. or lower, if desired.

Compounds of Formula B above are also produced during the reaction asdescribed above to produce compounds of Formula A, although the yield isusually very low unless sufficient polyol, i.e., at least about 2 molesper mole of hexahalocyclopentadiene, as well as sufiicient base, againat least about 2 moles per mole of hexahalocyclopentadiene, areemployed.

Using these proportions of reactants, good yields of compounds of theFormula B are produced and, while low temperatures such as thosedescribed above can be used, the reaction may also be carried out attemperatures up to about C. or higher and it is preferred to usetemperatures of at least about 50 C. The Formula B compounds are alsoconveniently made by reaction of compounds of the Formula A withadditional polyol in the presence of additional base, using temperaturesbetween about 40 C. and about 120 C. This reaction can be carried outwith a different alcohol from that used to make the compound of theFormula A; it may be any alcohol, either monohydric or polyhydric andhaving the hydroxyl groups either on adjacent or non-adjacent carbonatoms. For example, in addition to those polyols enumerated above,polyols such as 1,3-propanediol, 1,4- butanediol, 2,2-dimethyl 1,3propanediol, trimethylolpropane, pentaerythritol, polyethylene glycolsand the like, as well as monohydric alcohols such as methanol, ethanol,heptanol and octanol, and other alcohols of the formula:

where R and R are as above, can be employed. When Compound A is reactedfurther with a polyol having hydroxyls on adjacent carbon atoms, the Rgroup in Formula B has the structure:

litr 0GR2 O(|3Ra H where R R and R are again derived from the polyol andare as defined above. When, however, a monohydric alcohol or a polyolhaving hydroxyls on non-adjacent atoms is used in making the compoundsof the Formula B, the R group is of the structure:

where R and R are as defined above. In these instances, one hydroxylgroup from each of two alcohol molecules reacts with thehexahalocyclopentadiene nucleus, Whereas in the case of the polyolhaving adjacent hydroxyl groups, both hydroxyl groups reacting with thehexahalocyclopentadiene are attached to the same polyol molecule.

The compounds of Formula B can also be produced by changing the order ofreaction, that is, by first reacting hexahalocyclopentadiene with themonohydric alcohol to produce a compound of the structure:

and then reacting this compound with the polyol.

It may be noted that the double bond in Formula B is shown in the3-position. However, depending upon the particular reactants andreaction conditions, the double bond in all or part of the productobtained in particular cases may be in the 2-position. The compounds areconsidered equivalent for purposes of this invention, and names andformulas herein are intended to include both isomers as well as themixture.

The compounds of Formula C are also obtained from the reaction of polyolwith the hexahalocyclopentadiene in the manner used to produce compoundsof Formula A, if suflicient polyol and sutficient base are present.However, even utilizing excesses of the polyol and base, the yields ofcompounds of Formula C are quite low in any reasonable length of time.For this reason, compounds of Formula C are better produced indirectlyby reacting a preformed compound of Formula A with at least twoadditional moles of polyol in the presence of at least two additionalmoles of base, or by reacting a preformed compound of Formula B with atleast one additional mole of each of the polyol and the base. Thetemperature may vary from 80 C. up to about 140 C. or even higher. It isnoteworthy to observe that in the compounds of Formula C, the third moleof the polyol attaches to the hexahalocyclopentadiene nucleus in adifferent manner than the first two molecules, in that each of thehydroxyl groups from the third mole of polyol attaches to a differentcarbon atom.

The compounds of Formula D are dimers of the compounds of Formula A andare produced whenever a compound of Formula A is heated to a temperatureabove its melting point. The dimer is also obtained whenever a compoundof Formula A is dissolved in a solvent in which it has an appreciablesolubility, although relatively long periods of time, several days orlonger, are required for the dimerization unless the solution is heated.Some examples of such solvents which may be so employed to produce thesecompounds are chloroform, benzene, toluene, ethyl acetate andtetrahydrofuran. The dimerization of compounds of Formula A is quitesurprising and unexpected, since the most closely related knowncyclopentadiene derivatives do not form dimers.

It may be noted that the ranges of conditions and proportions whichproduce the several compounds'depicted above overlap. In such instances,mixtures of the different products may be obtained; however, by properchoice of the conditions and proportions, good yields of any of theabove compounds are achieved.

The several compounds to which this invention relates will be furtherdescribed by reference to the following examples; these examples, beingillustrative, should not be construed as limiting the invention to theirdetails.

Example I.1,2,3,4-tetrachloro-6,9-dioxa-1,3-

spiro [4.4] nonadiene A two-liter, round bottom flask was charged with 1mole of hexachlorocyclopentadiene. A solution of 137 grams (2.10 moles,percent purity) of potassium hydroxide in ethylene glycol (496.0 grams,8.0 moles) was added dropwise at 25 C. to 33 C. When two-thirds of theglycol solution had been added, there was one liquid phase and someprecipitated potassium chloride. The remainder of the solution was addedand the reaction mixture was stirred at 25 C. to 30 C. for 20 hours; thepH was then 8.0. One liter of water was added and the layers wereseparated. The water layer was extracted with ether and the combinedorganic layers were washed with saturated sodium chloride solution andthe organic solvent removed under vacuum. When the organic layer wasnearly evaporated to dryness, ligroin was added and the solution cooledto -78 C. and filtered. There was obtained 206 grams of the aboveproduct.

Analysis.Calculated for C H Cl O C, 32.01%; H, 1.54%; CI, 54.15%. Found:C, 31.97%; H, 1.63%; Cl. 54.02%.

Obviously, when hexabromocyclopentadiene is employed, the tetrabromoequivalent will be formed.

Example II.--1,2,3,4-tetrachloro-7-methyl-6,9-dioxa-1,3-spiro[4.4]nonadiene A three-necked, two-liter, round bottom flaskwas charged with 1 mole (73 grams) of hexachlorocyclopentadiene, 2 moles(152.0 grams) of 1,2-propanediol and 300 milliliters of dimethoxyethane.To this solution 2.0 moles (132.4 grams, 85 percent purity) of potassiumhydroxide were added in portions while the temperature was kept at 26 C.to 33 C. by external cooling. It took 45 minutes for the addition. Theheterogeneous mixture was stirred at 26 C. overnight; the resultantsolution had a pH of 8.5. To this solution, water was added and theorganic layer was washed with water six times, dissolved in ether andfiltered through Celite. After the solvent was removed at roomtemperature in vacuo, there was obtained 25 grams of crude product whichwas distilled to give pure 1,2,3,4-tetrachloro-7-methyl-6,9-dioxa-1,3-spiro[4.4]-nonadiene, boiling point 80 C. at 0.07 millimeter, asidentified by gas chromatographic analysis. Upon careful distillation,the pure sample boiled at 69 C. at 0.04 milliliter.

Analysis-Calculated for C H Cl O C, 34.82%; H, 2.19%; C1, 51.40%. Found:C, 34.82%; H, 2.32%; Cl, 51.38%.

The use of hexabromocyclopentadiene will produce 1,2,3,4-tetrabromo 7methyl 6,9 dioxa-1,3-spiro[4.4] nonadiene.

Example III.-1,2,3,4-tetrachloro-7,8-dimethyl-6,9-

dioxa-1,3-spiro [4.41nonadiene To a three-necked, two-liter, roundbottom flask containing grams (1.5 moles) of 2,3-butauediol, 273 grams(1 mole) of hexachlorocyclopentadiene and 300 milliliters ofdimethoxyethane, solid potassium hydroxide (132.4 grams, 2 moles, 85percent purity) was added in portions with external cooling, while thetemperature was kept at 30 C. The addition took 45 minutes and thereaction mixture was stirred overnight at 26 C. Water was then added,whereupon an oily product precipitated which was separated and washedwith water. Ether was added and the solution was washed with saturatedsodium chloride solution until neutral. After evaporation of the solventunder vacuum at room temperature, there remained a crude product, 10grams of which was distilled to give 6.65 grams of a fraction boiling at60 C. to 100 C. at 0.1 millimeter, which was recrystallized frompetroleum ether (boiling point 35 C. to 60C.) at solid carbon dioxidetemperature five times to give the pure product which melted at 40 C. to40.5 C.

Analysis.Calculated for C H Cl O C, 37.27%; H, 2.78%; Cl, 48.91%. Found:C, 37.84%; H, 3.05%; CI, 48.49%.

The use of hexabromocyclopentadiene will produce 1,2,3,4tetrabromo 7,8dimethyl 6,9 dioxa-1,3-spiro- [4.4]nonadiene.

To produce the compounds of this invention, the polyol must have atleast two hydroxyl groups on adjacent carbon atoms. If the only hydroxylgroups in the polyol are on non-adjacent carbon atoms, products of acompletely different class are obtained, as is disclosed in copendingapplication Ser. No. 234,847, filed Nov. 1, 1962, now U.S. Patent3,358,039. However, the polyol used herein may have hydroxyls onnon-adjacent carbon atoms in addition to those hydroxyls on adjacentcarbon atoms, and the products obtained are as described herein,although the yields may be reduced by the competing reaction takingplace with the adjacent hydroxyl groups. Set forth below is an exampleof the reaction using such a polyol.

Example IV.-7 (4'-hydroxybutyl)-l,2,3,4-tetrachloro-6,9-dioxaspiro[4.4]-nona-1,3-diene To a. two-liter, three-necked flaskwere added 675 grams (5 moles) of 1,2,6-hexanetriol and 64.4 grams (0.97mole, 85 percent purity) of solid potassium hydroxide in portions at 90C. to 100 C. The solution was cooled and hexachlorocyclopentadiene(137.0 grams, 0.50 mole) was added dropwise at 23 C. to 28 C. while theflask was cooled externally. After the addition, the reaction mixturewas stirred at 30 C. for 24 hours (pH was then 8.0). The product wasextracted with 500 milliliters of ligroin (boiling point 60 C. to 78 C.)to remove 19.2 grams of the unreacted hexachlorocyclopentadiene.Chloroform was added and the mixture was then washed with saturatedsodium chloride solution until neutral. The solvent was removed invacuum to give 148 grams of a mixture of 7(4 hydroxybutyl) 1,2,3,4tetrachloro- 6,9-dioxaspiro[4.4]-nona-1,3-diene, the desired product,and 5,5 bis(5,6 dihydroxyhexyloxy) 1,2,3,4tetrachloro-1,3-cyclopentadiene. The products were analyzed byultraviolet light absorption and infrared examination.

In a similar manner the following compounds are likewise formed:

1,2,3,4-tetrachloro-7,7,8-trimethyl-6,9-dioxa- 1,3 -spiro [4.4]nonadiene 1,2,3 ,4-tetrabromo-7 ,7 ,8-trimethyl-6,9-dioxa-1,3 -spiro[4.4] nonadiene 1,2,3 ,4-tetrachloro-7-cyclohexyl-6,9-dioxal ,3-spiro[4.4]

nonadiene 1,2,3,4-tetrabrmo-7-cyclohexyl-6,9-dioxa-1,3 -spiro [4.4]

nonadiene 1,2,3,4-tetrachloro-7-phenyl-6,9-dioxa-1,3-Spiro [4.4]

nonadiene 1,2,3 ,4-tetrabromo-7-phenyl-6,9-dioxa-1,3 -spiro [4.4]

nonadiene 1,2,3,4-tetrachloro-7-methoxy-8-methyl-6,9-dioxa-1,3-

spiro [4.4] nonadiene1,2,3,4-tetrabromo-7-methoxy-8-methy1-6,9-dioxa-1,3-

spiro [4.4] nonadiene1,2,3,4-tetrachloro-7-phenoxy-8-methyl-6,9-dioxa-1,3-

spiro[4.4] nonadiene1,2,3,4-tetrabromo-7-phenoxy-8-methyl-6,9-dioxa-1,3-

spiro [4.4] nonadiene The above examples illustrate the compounds of theinvention corresponding to Formula A. Below are several examples ofproducts corresponding to Formula B. Examples V to VII demonstrate thosecompounds of Formula B which are produced from polyols, whereas Examples8 and 9 demonstrate the similar compounds made from monohydric alcohols.

Example V.1,2,4-trichloro-3-ethylenedioxy-6,9-

dioxa-1spiro [4.4] nonene An ether solution of1,2,3,4-tetrachloro-6,9-dioxa-1,3- spiro[4.4]nonadiene (0.20 mole, 52.4grams) was added slowly at C. to a flask containing 74.4 grams (1.20moles) of ethylene glycol and 31.2 grams (0.60 mole, 85 percent purity)of potassium hydroxide. The ether was removed continuously during theaddition by distillation at 20 millimeters vacuum. After all of thenonadiene Was added and most of the ether was removed, the mixture wasstirred at 65 C. to C. for 22.5 hours. The reaction product was cooledslowly to room temperature, water was added, and the heterogenousmixture was filtered. A solid was collected by filtration and was thendistilled to give 34.4 grams of pure product, boiling point 120 C. to130 C. at 0.04 millimeter. It was identified by gas chromatographic andinfrared analysis, as well as chemical analysis.

Analysis.Calculated for C H Cl O C, 37.59%; H, 3.15%; Cl, 37.00%. Found:C, 37.95%; H, 3.46%; Cl, 37.48%.

The use of 1,2,3,4-tetrabromo-6,9-dioxa-1,3-Spiro[4.4] nonadieneproduces l,2,4-tribromo-3-ethylenedioxy-6,9- dioxa-l-spiro[4.4]nonene.

Example VI.-1,2,4-trichloro-3-'( 1,2-propylenedioxy)-7-methyl-6,9-dioxa-1-spiro [4.4]nonene A three-necked, five-liter flaskwas charged with 12.1 moles (920 grams) of propylene glycol. Potassiumhydroxide (10.7 moles, 600 grams, percent purity) was added in portionsuntil all was dissolved. To this solution, 575 milliliters ofdimethoxyethane and 250 milliliters of ligroin were added, and themixture was refluxed at 62 C. Hexachlorocyclopentadiene (2 moles, 545.6grams) was added dropwise to the refluxing mixture; the temperature wentto 64 C. After all of the hexachlorocyclopentadiene was added, themixture was stirred and refluxed at 59 C. for several hours whileremoving 35 milliliters of water. The product was then mixed with 1liter of water and neutralized with dilute hydrochloric acid. Theorganic layer was washed with water and dried on a steam bath in vacuum.The oily residue was distilled and 342.6 grams of the product wascollected at 0.1 to 0.45 millimeter. This crude product was redistilledto give 224.4 grams of the pure product, boiling point 102 C. at 0.038millimeter pressure.

Analysis.-Calculated for C H Cl O C, 41.86%; H, 4.15%; C], 33.70%.Found: C, 41.86%; H, 4.15%; Cl, 33.71%.

The use of hexabromocyclopentadiene produces 1,2,4- tribromo 3 (1,2propylenedioxy) 7 methyl 6,9- dioxa-l-spiro [4.4] nonene.

Example VII The same compound as in Example VI was also prepared byfurther reaction of 1,2,3,4-tetrachloro-7-methyl-6,9-dioxa-1,3-spiro[4.4] nonadiene with propylene glycol in the presenceof potassium hydroxide, as follows: Four grams of potassium hydroxidewere dissolved in milliliters of propylene glycol at 80 C. To thissolution was added a solution of 4.95 grams of 1,2,3,4-tetrachloro-7-methyl-6,9-dioxa-1,3-Spiro[4.4]nonadiene in 5.0 milliliters ofdimethoxyethane and the mixture was stirred for ExampleVIII.-3,3-dimethoxy-1,2,4-trichloro-6,9 dioxal-spiro [4.4 nonene Athree-necked, SOD-milliliter round bottom flask was charged with 54.4grams (1.7 moles) of methanol and 31.2 grams (0.6 mole, 85 percentpurity) of potassium hydroxide. At 65 C. to 70 C.,1,2,3,4-tetrachloro-6,9- dioxa-1,3-spiro[4.4]nonadiene (52.4 grams, 0.20mole) in 60 milliliters of dimethoxyethane was added dropwise. Thereaction mixture was stirred at 65 C. for 2 hours. Water and ether wereadded to the cooled product and the organic layer was washed with waterthree times, dried and distilled, yielding 54.5 grams of a fractionboiling at 88 C. to 90 C. at 0.03 to 0.035 millimeter. The distillatewas added to petroleum ether (boiling point 35 C. to 60 C.) and thecrystallized product was filtered. The solid, melting point 51 C. to 63C., was recrystallized three times from ligroin to give 29.5 grams ofthe product, which melted at 675 C. to 68.5 C.

Analysis.Calculated for C I-I Cl O C, 37.33%; H, 3.83%; Cl, 36.74%.Found: C, 37.73%; H, 3.85%; Cl, 36.89%.

The use of 1,2,3,4-tetrabromo-6,9-dioxa-1,3-spiro[4,4] nonadieneproduces 3,3 dimethoxy 1,2,4-tribromo-6,9- dioxa-l-spiro[4.4]nonene.

Example IX The same compound produced in Example VIII was made asfollows: Hexachlorocyclopentadiene was reacted with methanol in thepresence of potassium hydroxide to produce1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene (52.8 grams, 0.20mole), which was then added at 105 C. to a flask containing 74.4 grams(1.20 moles) of ethylene glycol and 31.2 grams (0.60 mole, 85 percentpurity) of potassium hydroxide. The mixture was stirred for 2 hours andfiltered; 12.5 grams of potassium chloride was separated. The filtratewas mixed with water and ether, and the ether layer was separated andwashed until neutral. Crystallization from ligroin gave 48.5 grams ofproduct, melting point 67 C. to 68.5 C. The 3,3-dimethoxy-l,2,4-trichloro-6,9-dioxa-l-spiro[4.4]nonene was identified by mixed meltingpoint, infrared spectra and gas chromatography.

The use of hexabromocyclopentadiene produces 3,3-dimethoxy-1,2,4-tribromo-6,9-dioxa-l-spiro [4.4]nonene.

In the manner of the above two-stage examples, the following compoundscan also be prepared by further reacting 1,2,3,4 tetrachloro 6,9dioxa-1,3-spiro[4.4]- nonadiene orl,2,3,4-tetrabromo-6,9dioxa-l,3-spiro[4.4]- nonadiene with theappropriate alcohol:

1,2,4-trichloro-3 1,2-hexanedioxy)-6,9-dioxa-1- spiro [4.4] nonene1,2,4-tribromo-3 1,2-hexanedioxy)-6,9-dioxa-lspiro [4.41nonene1,2,4-trichloro-3 cyclohexyl-1,2-ethanedioxy -6,9-

dioxa-l-spiro [4.4] nonene 1,2,4-tribromo-3 cyclohexyl-l ,Z-ethanedioxy)-6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-trichloro-3 pheny1-1,2-ethanedioxy) -6,9-

dioxa-l-spiro [4.41nonene 1,2,4-tribromo-3 (phenyl-1,2-ethanedioxy)-6,9-dioxa-1- spiro[4.4]nonene 1,2,4-trichloro-3(methoxy-2,3-propanedioxy) -6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-tribromo-3 methoxy-2, 3 -prop ane dioxy)-6,9-

dioxa-1-spiro[4.4] nonene 1,2,4-trichloro-3 (phenoxy-2,3-propanedioxy)-6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-tribromo-3 (phenoxy-2,3-propanedioxy)-6,9-dioxa- 1-spiro[4.4] nonene 1,2,4-trichloro-3(6-hydroxy-1,2-hexanedioxy) -6,9-

di0xa-1-spiro[4.4] nonene 1,2,4-tribromo-3 6-hydroxy-1,2-hexanedioxy)-6,9-dioxal-spiro [4.4]nonene" 1,2,4-trich1oro-3 3-bis(4-hydroxy-1-butoxy) 6,9-

dioxal-spiro [4.4] nonene 1,2,4-tribromo-3,3-bis (4-hydroxy-1-butoxy)-6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-trichloro-3 ,3 (dioctyloxy) -6,9-dioxa-1-spiro[4.4]nonene 1,2,4-tribromo-3,3 (dioctyloxy) -6,9-dioxa-1-spiro[4.4]-

nonene Examples X to XII illustrate the method of making thecompositions of Formula C. Examples XI and XII also demonstratereactions in which difierent polyols are used in successive steps toproduce compounds having diflerent substituents corresponding to RExample X.1,8-dichloro-7,9-bis(ethylenedioxy)- 2, S-dioxabicyclo [4.3.0]-nonane To a three-necked, l-liter flask there was added a solution of74.4 grams (1.2 moles) of ethylene glycol and 31.2 grams (0.6 mole,percent purity) of potassium hydroxide. A solution of1,2,44tetrachloro-3-ethylenedioxy- 6-9-dioxa-1-spiro[4.4]nonene (57.2grams, 0.20 mole) in milliliters of dimethoxyethane was added dropwiseat 117 C. to 120 C. while low-boiling solvent was constantly removed.The addition took 20 minutes and the mixture was refluxed at 120 C. for8 hours. Water was added and the product was filtered to give a crudeproduct melting at 114 C. to C. This solid was distilled and thefraction boiling at C. at 0.018 millimeter (45.05 grams) wasrecrystallized from acetonemethanol. The product obtained melted at142.5 C. to 143 C.

Analysis.Calculated =for C H CI O C, 42.19%; H, 4.51%; Cl, 22.65%.Found: C, 41.91%; H, 4.32%; Cl, 22.04%.

The use of 1,2,4-tetrabromo-3-ethylenedioxy-6,9 dioxa-1-spiro[4.4]nonene produces 1,8-dibromo-7,9-bis(ethylene-dioxy)-2,5-dioxabicyclo[4.3]nonane.

Example XI.-1,8-dichloro-7,9-bis(ethylenedioxy)-3- me thyl-2,5-dioxabicyclo [4.3 .0] nonane Hexachlorocyclopentadiene was reacted withethylene glycol in the presence of potassium hydroxide to produce1,2,3,4-tetrachloro-6,9-dioxa-1,3-spiro(4.4)nonadiene as in Example Iabove, and this product was reacted with additional ethylene glycol asin Example V to produce 1,2,4- trichloro-3-ethylenedioxy 6,9dioxa-l-spiro[4.4] nonene. One mole (28.73 grams) of this productdissolved in 50 milliliters of 1,2-dirnethoxyethane was added dropwiseto a flask containing a solution of 0.3 mole of potassium hydroxide (20grams, 85 percent purity) in 0.6 mole (45.6 grams) of propylene glycolat 120 C. The temperature was held at 120 C. for 8 hours and at roomtemperature overnight. Water was added and the oil layer whichprecipitated was separated and washed several times with water. Thewater layer was washed with ether and the 'ether added to the oil. Theoil was distilled and the crude product boiling at C. at 0.3 millimeterpressure was redistilled to yield 10.3 grams of pure product having aboiling point of 146 C. at 0.07 millimeter. The use of1,2,4-tribromo-3-ethylenedioxy-6,9 dioxa 1 spiro[4.4] nonene produces1,8 dibromo-7,9-bis(ethylenedioxy)-3-methyl-2,5-dioxabicyclo[4.3.0]nonane.

1 1 Example XII.1,8-dichloro-7,9-bis( 1,2-propylenedioxy)-2,5-dioxabicyclo- [4.3.0] nonane 1,2,4-trichloro-3-(1,2-proplyenedioxy)7 methyl 6,9- dioxa-1-spiro[4.4] nonene (0.1 mole, 31.6 grams) wasproduced from hexachlorocyclopentadiene and propylene glycol in themanner of Example VI above and added to a flask containing a solution of20 grams of potassium hydroxide (0.3 mole, 85 percent purity) in 37.2grams of ethylene glycol (0.6 mole) at 135 C. The mixture was stirred at135 C. to 140 C. for 8 hours. After standing at room temperatureovernight, water was added and the oil layer which separated was washedwith water several times. The water layer was washed with ether and theether added to the oil. Distillation produced 12 grams of crudematerial, which was redistilled to yield 11.7 grams of pure productboiling at 120 C. to 126 C. at 0.1 millimeter of pressure. The use of1,2,4-tribromo-3-(1,2- propylenedioxy)-7-methyl-6,9dioxa-l-spiro[4.4]nonene produces 1,8-dibromo-7,9-bis(1,2-propylenedioxy)-2,5-dioxabicyclo[4.3.0]nonane.

In the manner of Example XIII, the following compounds can also beprepared by further reacting 1,2,4- trichloro-3-(1,2-propylenedioxy) 7methyl-6,9-dixa-lspiro[4.4]nonene or1,2,4-tribromo-3-(1,2-propylenedioxy)-7-methyl-6,9-dioxa-l-spiro[4.4]nonenewith the appropriate hydroxy compound: 1,8-dichloro-7,9-bis(ethylenedioxy) -3 -methyl-2,5-dioxabicyclo [4.3 .0] nonane1,8-dibromo-7,9-bis(ethylenedioxy)-3-methyl-2,5-dioxabicyclo[4.3.0]nonane l, 8-dichloro-7,9-bis (ethylenedioxy)-3-octyl-2,5-dioxabicyclo[4.3.0]nonane 1,8-dibromo-7,9-bis(ethylenedioxy) -3-octyl-2,5-dioxabicyclo [4.3.0]nonane1,8-dichloro-7,9-bis(ethylenedioxy)-3-cyclohexyl-2,5-dioxabicyclo[4.3.0]nonene l,8-dibromo-7,9-bis (ethylenedioxy)-3-cyclohexyl-2,5-dioxabicyclo[4.3.0]nonene 1,8-dichloro-7,9-bis(ethylenedioxy) -3-phenyl-2,5-dioxabicyclo[4.3.0]nonane1,8-dibromo-7,9-bis (ethylenedioxy) -3-pheny1-2,5-dioxabicyclo[4.3.0]nonane 1, 8-dichloro -7 ,9-bis (ethylenedioxy) -3-methoxy-2,5-dioxabicyclo [4.3.0]nonane1,8-dibromo-7,9-bis(ethylenedioxy)-3-mcthoxy-2,5-dioxabicyclo[4.3.0]nonane 1,8-dichloro-7,9-bis (ethylenedioxy) -3 -phenoxy-4-methyl-2,5-dioxabicyclo[4.3.01nonane 1,8-dibromo-7,9-bis (ethylenedioxy)-3-phenoxy-4-methyl- 2,5-dioxabicyclo[4.3.0] nonane1,8-dichloro-7,9-bis(ethylenedioxy) -3- (4-hydroxypropyl)2,5-dioxabicyclo[4.3.0Jnonane 1,8-dibromo-7,9-bis (ethylenedioxy)-3,4hydroxypropyl) 2,5-dioxabicyclo [4.3.0]nonane The following examplesdemonstrate compounds of Formula A, which are dimers of compounds ofFormula A. Example XIII illustrates the manner in which such compoundsare made by producing a compound of Formula A and then heating it insolution, while Example XIV illustrates the preparation of a similarcompound by heating the corresponding compound of Formula A to atemperature above its melting point.

Example XIII.1,2,3,4,5,6,7,8-octachloro 3,7-tricyclo [4.3 .01decadiene-9, l0-dione di( glycerine-1,2 diketal A three-necked, S-literflask was charged with 32 moles of glycerine (2944 grams). Potassiumhydroxide (8.40 moles, 538 grams) was added in portions. To thissolution at 85 C., 4 moles (1091 grams) of hexachlorocyclopentadiene wasadded. The reaction mixture was stirred at 85 C. to 90 C. for 17.5hours, at which time the mixture was acidic. An additional 27 grams ofsolid potassium hydroxide was added. which was consumed in hours.Another 27 grams of potassium hydroxide was added, which in turn wasconsumed in 21.0 hours. The reaction mixture was then cooled to roomtemperature, filtered and a small amount of choloroform was added. Themixture was steam distilled to remove the unreacted starting materialand low-boiling impurities; during the distillation the reaction mixturewas at a temperature of about C. whereupon the initial productdimerized. The residue was then separated from water and dried at C. toC. at 0.1 millimeter. The yield of 1,2,3,4-tetrachlorocyclopentadiene-l-one glycerine ketal dimer was 842 grams.

Example XIV.1,2,3,4,5,6,7,8-octachloro-3,7-tricyclo [4.301]decadiene-9,1O-dione di (2,3 -butylene glycol)diketal Five grams ofl,2,3,4 tetrachloro 7,8-dimethyl-6,9- dioxa-1,3-spiro[4.4]nonadiene washeated in a test tube on a steam bath for 5 hours to give a hard resin.This resin was distilled; the fraction boiling at 200 C. to 220 C. at0.10 millimeter was found to be a mixture of the isomeric diketals. Themixture of isomers was dissolved in ether and an isoluble solid wasfiltered and collected. This solid was then crystallized from chloroformand ligroin (boiling point 85 C. to 100 C.) to give a product having amelting point of 192 C. to 194 C. This was one solid isomer of thediketal.

Analysis-Calculated for C H C1 0 C, 37.27%; H, 2.78%; Cl. 48.91%. Found:C, 36.81%; H, 2.35%; Cl, 49.84%.

All the compounds corresponding to Formula A recited hereinabove producetheir dimers in an equivalent manner, for example:

1,2,3,4,5,6,7,8-octachloro-3 ,7 -tricyclo [4.3.0. 1J-decadiene-9,10-dione di(cyclohexyl-LZ-ethylene glycol) diketal1,2,3,4,5,6,7,8-octabromo-3,7-tricyclo [4.3.0.1 ]-decadiene-9, lO-di-one di(cyclohexyl-1,2-ethyleneglycol) diketal1,2,3,4,5,6,7,8-octachl0r0-3,7-tricyclo [4.3 .01 -decadiene-9,l0-dionedi(phenyl-1,2-ethylene glycol)diketal1,2,3,4,5,6,7,8-octabromo-3,7-tricyclo[4.3.0.1 ]-decadiene-9,l0-dionedi(phenyl-1,2-'ethylene glycol) diketal1,2,3,4,5,6,7,8-octachloro-3,7-tricyclo[4.3 01 -decadiene-9, l0-dionedi( 1-methoxy-2,3-propyleneglycol) diketal1,2,3,4,5,6,7,8-octabromo-3,7-tricyclo [4.3.0.1 ]-decadiene-9,10-dionedi( l-methoxy-2,3-propyleneglycol) diketal1,2,3,4,5,6,7,8-octachIoro-3,7-tricyclo[4.3.01 ]-dccadiene-9, 1 O-dionedi( 1-phenoxy-2,3-propylene glycol diketal1,2,3,4,5,6,7,8-octabromo-3,7-tricyclo[4.3.0.1 ]-decadiene-9,10-dionedi(1-phenoxy-2,3-propylene glycol) diketal1,2,3,4,5,6,7,8-octachloro-3,7-tricyclo[4.3.0. 1 [-decadiene-9,10-dionedi(6-hydroxy-1,2-hexane glycol) diketal1,2,3,4,5,6,7,8-octabromo-3,7-tricyclo [4.3.0.1 ]-decadiene-9-10-dionedi(6-hydroxy-1,2-hexane glycol) diketal While the examples show specificreactants, all the polyols and alcohols enumerated in the specification,as well as not specifically enumerated, are reactive in a similar manerto produce compounds within the scope of the invention.

Likewise, while the above examples demonstrate the invention usinghexachlorocyclopentadiene, other hexah'alocyclopentadienes, such ashexabromocyclopentadiene, and including cyclopentadiene derivativescontaining different halogens in the same molecule, such as1,2-dibr0mo-3,4,5,S-tetrachlorocyclopentadiene and2,3-di'bromo-1,4,5,S-tetrachlorocyclopentadiene are also contemplatedfor use herein and produce corresponding halogencontaining products.Similarly, although for clarity the invention has been described andexemplified using a single alcohol in each reaction or step, mixtures ofpolyols or, in the appropriate instance, mixtures of monohydroxyalcohols can also be employed.

The compounds of this invention are useful in several variedapplications. They find utility, for example, as insecticides andnematocides. To exemplify their activity in this regard, the compound ofExample VIII, applied as a 2.5 percent solution in acetone, topically tothe thorax of houseflies (Wilson), efi'ectively killed the flies. Thenematocidal activity of the compounds described herein was shown bytests such as one in which the compound of Example I was applied as asolution in an acetonewater mixture to a suspension of Panagrellusnematodes in water (500 to 750 nematodes per milliliter); it was foundthat this treatment was extremely effective in destroying the nematodes,even using very low concentrations of the compound, e.g., .0001 percent.

In addition to their use as insecticides and in related applications,the compounds of the invention have various other uses, depending upontheir particular properties. For example, compounds of Formula A andFormula B react with olefinic compounds to produce Diels-Alder additionproducts that can 'be utilized in making resinous materials in whichhalogens are sought to be introduced. For example, the reaction of thecompound of Example H with maleic anhydride results in a material fromwhich polyester resins can be obtained. Similarly, the reactions ofcompounds of Formula D with reactive dienes such as cyclopentadieneresult in products which, after oxidation, can be used to producepolyester resins.

In many instances, the halogen contents of the various compounds aresuch as to produce specifically desired results. For instance, compoundsof Formula C are quite useful as plasticizers in systems wherein a highbut limited amount of halogen is desired, and compounds of Formula D,which have extremely high halogen content, can be added to conventionalfoam-producing compositions to increase the fire-retardancy of the foamsproduced therefrom.

According to the provisions of the patent statutes, there are describedabove the invention and what are now considered to be its bestembodiments. However, within the scope of the appended claims, it is tobe understood that the invention may be practiced otherwise than asspecifically described.

I claim:

1. A compound of the formula:

where X is chlorine or bromine, R R and R are each selected from theclass consisting of hydrogen and alkyl, cycloalkyl, phenyl, alkoxyalkyl,phenyloxyalkyl and hydroxyalkyl groups containing 1 to 10 carbon atoms.

2. A compound as in claim 1 wherein R R and R are selected from thegroup consisting of hydrogen and alkyl containing 1 to 10 carbon atoms.

3. A compound as in claim 2 Where X is chlorine.

4. The compound of claim 1 in which X is chlorine.

5. A compound as in claim 1 which is 1,2,3,4,5,6,7,8- octachloro 3,7tricyclo[4.3.0.1 ]decadiene 9,10- dione di( glycerine-1,2)diketal.

6. A compound as in claim 1 which is 1,2,3,4,5,6,7,8- octachloro 3,7tricyclo[4.3.0.1 ]decadiene 9,10- dione di(2,3-butylene glycol)diketal.

References Cited UNITED STATES PATENTS 2,905,697 9/1959 Schmerling260340.3

ALEX MAZEL, Primary Examiner.

I. H. TURNIPSEED, Assistant Examiner.

US. Cl. X.R.

